Laundry detergent compositions with cellulosic polymers to provide appearance and integrity benefits to fabrics laundered therewith

ABSTRACT

Disclosed are detergent compositions and methods which utilize certain modified cellulose ethers as fabric treatment agents that can impart fabric appearance and integrity benefits to fabrics and textiles laundered in washing solutions which contain such agents. Such modified cellulose ether fabric treatment agents are those having selected types and amounts of anhydroglucose ring substituents in order to render them nonionic, cationic or anionic in nature.

TECHNICAL FIELD

The present invention relates to heavy duty laundry detergentcompositions, in either liquid or granular form, which contain certaintypes of modified cellulose ether materials to impart appearance andintegrity benefits to fabrics and textiles laundered in washingsolutions formed from such compositions.

BACKGROUND OF THE INVENTION

It is, of course, well known that alternating cycles of using andlaundering fabrics and textiles, such as articles of worn clothing andapparel, will inevitably adversely affect the appearance and integrityof the fabric and textile items so used and laundered. Fabrics andtextiles simply wear out over time and with use. Laundering of fabricsand textiles is necessary to remove soils and stains which accumulatetherein and thereon during ordinary use. However, the launderingoperation itself over many cycles, can accentuate and contribute to thedeterioration of the integrity and the appearance of such fabrics andtextiles.

Deterioration of fabric integrity and appearance can manifest itself inseveral ways. Short fibers are dislodged from woven and knitfabric/textile structures by the mechanical action of laundering. Thesedislodged fibers may form lint, fuzz or “pills” which are visible on thesurface of fabrics and diminish the appearance of newness of the fabric.Further, repeated laundering of fabrics and textiles, especially withbleach-containing laundry products, can remove dye from fabrics andtextiles and impart a faded, worn out appearance as a result ofdiminished color intensity, and in many cases, as a result of changes inhues or shades of color.

Given the foregoing, there is clearly an ongoing need to identifymaterials which could be added to laundry detergent products that wouldassociate themselves with the fibers of the fabrics and textileslaundered using such detergent products and thereby reduce or minimizethe tendency of the laundered fabric/textiles to deteriorate inappearance. Any such detergent product additive material should, ofcourse, be able to benefit fabric appearance and integrity withoutunduly interfering with the ability of the laundry detergent to performits fabric cleaning function. The present invention is directed todetergent compositions containing certain types of cellulosic materialsthat perform in this desired manner.

SUMMARY OF THE INVENTION

The laundry detergent compositions herein comprise from about 1% to 80%by weight of a detersive surfactant, from about 0. 1% to 80% by weightof an organic or inorganic detergency builder and from about 0. 1% to 8%by weight of certain types of modified cellulose ether fabric treatmentagents. The detersive surfactant and detergency builder materials can beany of those useful in conventional laundry detergent products. Themodified cellulose ether materials are those which have a molecularweight of from about 10,000 to 2,000,000 and are comprised of repeatingsubstituted anhydroglucose units corresponding to the general StructuralFormulas Nos. I, II and III set forth hereinafter in the “DetailedDescription of the Invention” section. (In the Structural Formulashereinafter set forth, substituents are shown in specific positions onthe anhydroglucose rings which repeat to form the substituted celluloseether polymers. It should be understood that this is for illustrationpurposes only and that such substituents may be found on any of thecarbon atoms of the anhydroglucose rings.)

One useful type of cellulose ethers comprises hydrophobically-modified,nonionic materials with anhydroglucose ring alkyl substitution rangingfrom about 0.1% to 5% by weight of the cellulose ether. Ringsubstituents are alkoxylated in amounts ranging from about 1 to 20moles.

A second useful type of cellulose ether comprises cationic celluloseether materials which may have anhydroglucose ring alkyl substitutionranging from about 0.1% to 5% by weight of the cellulose ether.Anhydroglucose ring substituents contain from about 1 to 20 moles ofalkoxylation and from about 0.005 to 0.5 moles of quaternary ammoniumcationic moieties.

A third type of cellulose ether comprises anionic cellulose ethermaterials which may have anhydroglucose ring alkyl substitution rangingfrom about 0.1% to 5% by weight of the cellulose ether. Theanydroglucose rings in such anionic materials also have a degree ofcarboxymethyl substitution ranging from about 0.05 to 2.5. Combinationsof the nonionic, cationic and anionic modified cellulose ethers can alsobe employed.

In its method aspect, the present invention relates to the laundering ortreating of fabrics and textiles in aqueous washing or treatingsolutions formed from effective amounts of the detergent compositionsdescribed herein, or formed from the individual components of suchcompositions. Laundering of fabrics and textiles in such washingsolutions, followed by rinsing and drying, imparts fabric appearancebenefits to the fabric and textile articles so treated. Such benefitscan include improved overall appearance, pill/fuzz reduction,antifading, improved abrasion resistance, and/or enhanced softness.

DETAILED DESCRIPTION OF THE INVENTION

As noted, the laundry detergent compositions of the present inventionessentially contain detersive surfactant, detergent builder and certainmodified cellulose ether fabric treatment agents which serve to enhancefabric appearance and integrity upon use of the detergent compositionsto launder fabrics and textiles. Each of these essential detergentcomposition components, as well as optional ingredients for suchcompositions and methods of using such compositions, are described indetail as follows: All percentages and ratios given are by weight unlessother specified.

A) Detersive Surfactant

The detergent compositions herein essentially comprise from about 1% to800% by weight of a detersive surfactant. Preferably such compositionscomprise from about 5% to 50% by weight of this surfactant. Detersivesurfactants utilized can be of the anionic, nonionic, zwitterionic,ampholytic or cationic type or can comprise compatible mixtures of thesetypes. Detergent surfactants useful herein are described in U.S. Pat.No. 3,664,961, Norris, issued May 23, 1972, U.S. Pat. No. 3,919,678,Laughlin et al., issued Dec. 30, 1975, U.S. Pat. No. 4,222,905,Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy,issued Dec. 16, 1980. All of these patents are incorporated herein byreference. Of all the surfactants, anionics and nonionics are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term “alkyl” is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants are a) the sodium, potassium andammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈ carbon atoms) such as those produced by reducingthe glycerides of tallow or coconut oil; b) the sodium, potassium andammonium alkyl polyethoxylate sulfates, particularly those in which thealkyl group contains from 10 to 22, preferably from 12 to 18 carbonatoms, and wherein the polyethoxylate chain contains from 1 to 15,preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassiumalkylbenzene sulfonates in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁-₁₃ LAS.

Preferred nonionic surfactants are those of the formula R¹(OC₂H₄)_(n)OH,wherein R¹ is a C₁₀-C₁₆ alkyl group or a C₈-C₁₂ alkyl phenyl group, andn is from 3 to about 80. Particularly preferred are condensationproducts of C₁₂-C₁₅ alcohols with from about 5 to about 20 moles ofethylene oxide per mole of alcohol, e.g., C₁₂-C₁₃ alcohol condensed withabout 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable nonionic surfactants include polyhydroxy fatty acidamides of the formula:

wherein R is a C₉₋₁₇ alkyl or alkenyl, R₁ is a methyl group and Z isglycityl derived from a reduced sugar or alkoxylated derivative thereof.Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methylN-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acidamides are known and can be found in Wilson, U.S. Pat. No. 2,965,576 andSchwartz, U.S. Pat. No. 2,703,798, the disclosures of which areincorporated herein by reference.

B) Detergent Builder

The detergent compositions herein also essentially comprise from about0.1% to 80% by weight of a detergent builder. Preferably suchcompositions in liquid form will comprise from about 1% to 10% by weightof the builder component. Preferably such compositions in granular formwill comprise from about 1% to 50% by weight of the builder component.Detergent builders are well known in the art and can comprise, forexample, phosphate salts as well as various organic and inorganicnonphosphorus builders.

Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates, i.carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassium,lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid. Other suitablepolycarboxylates for use herein are the polyacetal carboxylatesdescribed in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 toCrutchfield et al, and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 toCrutchfield et al, both of which are incorporated herein by reference.Particularly preferred polycarboxylate builders are the oxydisuccinatesand the ether carboxylate builder compositions comprising a combinationof tartrate monosuccinate and tartrate disuccinate described in U.S.Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure ofwhich is incorporated herein by reference.

Examples of suitable nonphosphorus, inorganic builders include thesilicates, aluminosilicates, borates and carbonates. Particularlypreferred are sodium and potassium carbonate, bicarbonate,sesquicarbonate, tetraborate decahydrate, and silicates having a weightratio of SiO₂ to alkali metal oxide of from about 0.5 to about 4.0,preferably from about 1.0 to about 2.4. Also preferred arealuminosilicates including zeolites. Such materials and their use asdetergent builders are more fully discussed in Corkill et al, U.S. Pat.No. 4,605,509, the disclosure of which is incorporated herein byreference. Also, crystalline layered silicates such as those discussedin Corkill et al, U.S. Pat. No. 4,605,509, incorporated herein byreference, are suitable for use in the detergent compositions of thisinvention.

C) Modified Cellulosic Polymers

The third essential component of the detergent compositions hereincomprises one or more modified cellulosic polymers. Such materials havebeen found to impart a number of appearance benefits to fabrics andtextiles laundered in aqueous washing solutions formed from detergentcompositions which contain such modified cellulosic materials. Suchfabric appearance benefits can include, for example, improved overallappearance of the laundered fabrics, reduction of the formation of pillsand fuzz, protection against color fading, improved abrasion resistance,etc. The modified cellulosic polymers used in the compositions andmethods herein can provide such fabric appearance benefits withacceptably little or no loss in cleaning performance provided by thelaundry detergent compositions into which such materials areincorporated.

The modified cellulosic polymers useful herein may be of the nonionic,cationic or anionic types, or the modified cellulosic polymericcomponent of the compositions herein may comprise combinations of thesecellulosic polymer types. The modified cellulosic polymer component ofthe compositions herein will generally comprise from about 0.1% to 8% bythe weight of the composition. More preferably, such modified cellulosicmaterials will comprise from about 0.5% to 4% by weight of thecompositions, most preferably from about 1% to 3%.

One suitable type of modified cellulosic polymer for use hereincomprises hydrophobically-modified, nonionic cellulose ethers having amolecular weight of from about 10,000 to 2,000,000, preferably fromabout 50,000 to 1,000,000. The hydrophobically-modified nonionicmaterials have repeating, substituted anhydroglucose units whichcorrespond to the general Structural Formula No. I as follows:

In Structural Formula No. I, R is a combination of H and C₈-C₂₄ alkyl,preferably C₈-C₁₆ alkyl. Alkyl substitution on the anhydroglucose ringsof the polymer ranges from about 0. 1% to 5% by weight, more preferablyfrom about 0.2lo to 2% by weight, of the polymer material. Also, inStructural Formula No. I, R¹ is H or methyl, and x ranges from about 1to 20, preferably from about 1 to 10.

The hydrophobically-modified nonionic cellulose ethers of StructuralFormula No. I include those which are commercially available and alsoinclude materials which can be prepared by conventional chemicalmodification of commercially available materials. Commercially availablecellulose ethers of the Structural Formula No. I type include Polysurf67, Natrosol Plus 430 and Natrosol Plus 330, all marketed by Hercules,Inc.

Another suitable type of modified cellulosic polymer for use hereincomprises certain cationic cellulose ethers, which may or may not behydrophobically-modified, having a molecular weight of from about 10,000to 2,000,000, more preferably from about 10,000 to 1,000,000. Thesecationic materials have repeating substituted anhydroglucose units whichcorrespond to the general Structural Formula No. II as follows:

In Structural Formula No. II, R is H or C_(g)-C₂₄ alkyl, preferablyC₈-C₁₆ alkyl. Alkyl substitution on the anhydroglucose rings of thepolymer ranges from about 0.1% to 5% by weight, more preferably fromabout 0.2% to 2% by weight, of the polymeric material. Also, inStructural Formula No. II, R² is CH₂CHOHCH₂ or C₈-C₂₄ alkyl, preferablyC₈-C₁₆ alkyl. R³, R⁴ and R⁵ are each independently methyl, ethyl orphenyl. R⁶ is H or methyl. Further, in Structural Formula No. II, xranges from about 1 to 20, preferably from about 1 to 10; and y rangesfrom about 0.005 to 0.5, preferably from about 0.005 to 0.1; and Z isCl⁻ or Br⁻.

The cationic cellulose ethers of Structural Formula No. II likewiseinclude those which are commercially available and further includematerials which can be prepared by conventional chemical modification ofcommercially available materials. Commercially available celluloseethers of the Structural Formula No. 1 type include the JR 30M, JR 400,JR 125, LR 400 and LK 400 UCARE polymers, all marketed by Union CarbideCorporation.

A third type of suitable modified cellulose polymers for use hereincomprises certain anionic cellulose ethers, which also may or may not behydrophobically-modified, having a molecular weight of from about 10,000to 2,000,000, more preferably from about 50,000 to 1,000,000. Theseanionic materials have repeating substituted anhydroglucose units whichcorrespond to general Structural Formula No. III as follows:

In Structural Formula No. III, R is a combination of H and a) CH₂COOAand, optionally, b) C₂-₂₄, preferably C₂-C₁₆, alkyl, with A being Na orK. Alkyl substitution on the anhydroglucose rings of the polymer rangesfrom about 0.1% to 5% by weight, more preferably from about 0.2% to 2%by weight, of the polymer material. The anionic cellulose ethers alsohave a degree of carboxymethyl substitution which ranges from about 0.05to 2.5, more preferably from about 0.1 to 1.0.

The anionic cellulose ethers of Structural Formula No. III also includethose materials which are commercially available and further includethose which can be prepared by conventional chemical modification ofcommercially available materials. Commercially available celluloseethers of the Structural Formula No. III include CMC 7H, CMC 99-7M andCMC 99-7L, all marketed by Hercules, Inc. and CMC D72, CMC D65 and CMCDHT, all marketed by Penn Carbose.

The commercially available cellulose ether materials useful herein arethemselves derived from suitable natural sources of cellulose. Suchsources include, for example, cotton linters and other vegetabletissues. The modified cellulose ethers used in this invention aregenerally all water-soluble materials. They can therefore be utilizedfor detergent composition preparation in the form of aqueous solutionsof the kin such cellulosic polymers if desired.

D) Optional Detergent Ingredients

In addition to the essential surfactants, builders and modified celloseethers hereinbefore described, the detergent composition of the presentinvention can also include any number of additional optionalingredients. These include conventional detergent composition componentssuch as bleaches and bleach activators, enzymes and enzyme stabilizingagents, suds boosters or suds suppressers, anti-tarnish andanticorrosion agents, soil suspending agents, soil release agents,germicides, pH adjusting agents, non-builder alkalinity sources,chelating agents, organic and inorganic fillers, solvents, hydrotropes,optical brighteners, dyes and perfumes.

A preferred optional ingredients for incorporation into the detergentcompositions herein comprises a bleaching agent, e.g., a peroxygenbleach. Such peroxygen bleaching agents may be organic or inorganic innature. Inorganic peroxygen bleaching agents are frequently utilized incombination with a bleach activator.

Useful organic peroxygen bleaching agents include percarboxylic acidbleaching agents and salts thereof Suitable examples of this class ofagents include magnesium monoperoxyphthalate hexahydrate, the magnesiumsalt of metachloro perbenzoic acid, 4-nonylamino4-oxoperoxybutyric acidand diperoxydodecanedioic acid. Such bleaching agents are disclosed inU.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European PatentApplication EP-A-133,354, Banks et al., Published Feb. 20, 1985; andU.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6,1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used, generally inparticulate form, in the detergent compositions herein. Inorganicbleaching agents are in fact preferred. Such inorganic peroxygencompounds include alkali metal perborate and percarbonate materials. Forexample, sodium perborate (e.g. mono or tetra-hydrate) can be used.Suitable inorganic bleaching agents can also include sodium or potassiumcarbonate peroxyhydrate and equivalent “percarbonate” bleaches, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) canalso be used. Frequently inorganic peroxygen bleaches will be coatedwith silicate, borate, sulfate or water-soluble surfactants. Forexample, coated percarbonate particles are available from variouscommercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaching agents, e.g., the perborates, thepercarbonates, etc., are preferably combined with bleach activators,which lead to the in situ production in aqueous solution (i.e., duringuse of the compositions herein for fabric laundering/bleaching) of theperoxy acid corresponding to the bleach activator. Various non-limitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, IssuedApr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1,1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) andtetraacetyl ethylene diamine (TAED) activators are typical andpreferred. Mixtures thereof can also be used. See also the hereinbeforereferenced U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Other useful amido-derived bleach activators are those of the formulae:

R¹N(R⁵)C(O)R²C(O)L or R₁C(O)N(R⁵)R²C(O)L

wherein R₁ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate andmixtures thereof as described in the hereinbefore referenced U.S. Pat.No. 4,634,551.

Another class of useful bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al. in U.S. Pat. No. 4,966,723, IssuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is:

Still another class of useful bleach activators includes the acyl lactamactivators, especially acyl caprolactams and acyl valerolactams of theformulae:

wherein R⁶ is H or an alkyl aryl, alkoxyaryl, or alkaryl groupcontaining from 1 to about 12 carbon atoms. Highly preferred lactamactivators include benzoyl caprolactam, octanoyl caprolactam,3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoylvalerolactam, nonanoyl valerolactam, decanoyl valerolactam, undecenoylvalerolactan, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.See also U.S. Pat. No. 4,545,784, Issued to Sanderson, Oct. 8, 1985,incorporated herein by reference, which discloses acyl caprolactams,including benzoyl caprolactam, adsorbed into sodium perborate.

If utilized, peroxygen bleaching agent will generally comprise fromabout 2% to 30% by weight of the detergent compositions herein. Morepreferably, peroxygen bleaching agent will comprise from about 2% to 20%by weight of the compositions. Most preferably, peroxygen bleachingagent will be present to the extent of from about 3% to 15% by weight ofthe compositions herein. If utilized, bleach activators can comprisefrom about 2% to 10% by weight of the detergent compositions herein.Frequently, activators are employed such that the molar ratio ofbleaching agent to activator ranges from about 1:1 to 10:1, morepreferably from about 1.5:1 to 5:1.

Another highly preferred optional ingredient in the detergentcompositions herein is a detersive enzymes component. Enzymes can beincluded in the present detergent compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, cellulases, peroxidases,and mixtures thereof of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin. Preferred selections are influencedby factors such as pH-activity and/or stability optima, thermostability,and stability to active detergents, builders and the like. In thisrespect bacterial or fungal enzymes are preferred, such as bacterial8amylases and proteases, and fungal cellulases.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry detergentcomposition. Preferred enzymes for laundry purposes include, but are notlimited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levelssufficient to provide a “cleaning-effective amount”. The term“cleaning-effective amount” refers to any amount capable of producing acleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as fabrics. In practicalterms for current commercial preparations, typical amounts are up toabout 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzymeper gram of the detergent composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition. Higher active levels may be desirablein highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble . When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 10. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P “Amano,” or “Amano-P.” Other suitable commerciallipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein.

The enzyme-containing compositions herein may optionally also comprisefrom about 0.001% to about 10%, preferably from about 0.005% to about8%, most preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

E) Detergent Composition Preparation

The detergent compositions according to the present invention can be inliquid, paste or granular forms. Such compositions can be prepared bycombining the essential and optional components in the requisiteconcentrations in any suitable order and by any conventional means.

Granular compositions, for example, are generally made by combining basegranule ingredients (e.g. surfactants, builders, water, etc.) as aslurry, and spray drying the resulting slurry to a low level of residualmoisture (5-12%). The in remaining dry ingredients can be admixed ingranular powder form with the spray dried granules in a rotary mixingdrum and the liquid ingredients (e.g. organic solutions of the essentialcellulosic polymers, enzymes, binders and perfumes) can be sprayed ontothe resulting granules to form the finished detergent composition.Granular compositions according to the present invention can also be in“compact form”, i.e. they may have a relatively higher density thanconventional granular detergents, i.e. from 550 to 950 g/l. In suchcase, the granular detergent compositions according to the presentinvention will contain a lower amount of “inorganic filler salt”,compared to conventional granular detergents; typical filler salts arealkaline earth metal salts of sulphates and chlorides, typically sodiumsulphate; “compact” detergents typically comprise not more than 10%filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in“compact form”, in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents.

Addition of the cellulose ether component to liquid detergentcompositions of this invention may be accomplished by simply mixing intothe liquid dertergent aqueous solutions of the desired cellulose ethers.Cellulose ethers can alter the viscosity or other rheologicalcharacteristics of liquid detergent products. It may therefore benecessary to compensate for any rheological changes in the liquiddetergent product brought about by cellulose ether addition by alteringthe type and amount of hydrotropes and/or solvents that are used.

F) Fabric Laundering Method

The present invention also provides a method for laundering fabrics in amanner which imparts fabric appearance benefits provided by thecellulosic polymers used herein. Such a method employs contacting thesefabrics with an aqueous washing solution formed from an effective amountof the detergent compositions hereinbefore described or formed from theindividual components of such compositions Contacting of fabrics withwashing solution will generally occur under conditions of agitationalthough the compositions of the present invention may also be used toform aqueous unagitated soaking solutions for fabric cleaning andtreatment.

Agitation is preferably provided in a washing machine for good cleaning.Washing is preferably followed by drying the wet fabric in aconventional clothes dryer. An effective amount of the liquid orgranular detergent composition in the aqueous wash solution in thewashing machine is preferably from about 500 to about 7000 ppm, morepreferably from about 1000 to about 3000 ppm.

G) Fabric Conditioning

The modified cellulose ethers hereinbefore described as components ofthe laundry detergent compositions herein may also be used to treat andcondition fabrics and textiles in the absence of the surfactant andbuilder components of the detergent composition embodiments of thisinvention. Thus, for example, a fabric conditioning compositioncomprising only the modified cellulose ethers themselves, or comprisingan aqueous solution of the modified cellulose ethers, may be addedduring the rinse cycle of a conventional home laundering operation inorder to impart the desired fabric appearance and integrity benefitshereinbefore described.

EXAMPLES

The following examples illustrate the compositions and methods of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention.

Example I Liquid Detergent Test Composition Preparation

Several heavy duty liquid detergent compositions are prepared containingvarious modified cellulosic polymers. Such liquid detergent compositionsall have the following basic formula:

TABLE A Component Wt. % C₁₂₋₁₅ alkyl ether (2.5) sulfate  38 C₁₂ glucoseamide  6.86 Citric Acid  4.75 C₁₂₋₁₄ Fatty Acid  2.00 Enzymes  1.02 MEA 1.0 Propanediol  0.36 Borax  6.58 Dispersant  1.48 Na Toluene Sulfonate 6.25 Modified Cellulosic Polymer (if present)  2.0 Dye, Perfume,Brighteners, Preservatives, Suds Suppressor, Balance other Minors, Water100%

Example II Granular Detergent Test Composition Preparation

Several heavy duty granular detergent compositions are preparedcontaining various modified cellulosic polymers. Such granular detergentcompositions all have the following basic formula:

TABLE B Component Wt. % C₁₂ Linear alkyl benzene sulfonate  9.31 C₁₄₋₁₅alkyl ether (0.35 EO) sulfate  12.74 Zeolite Builder  27.79 SodiumCarbonate  27.31 PEG 4000  1.60 Dispersant  2.26 C₁₂₋₁₃ AlcoholEthoxylate (9 EO)  1.5 Sodium Perborate  1.03 Soil Release Polymer  0.41Enzymes  0.59 Modified Cellulosic Polymer (if present)  2.5 Perfume,Brightener, Suds Suppressor, Other Minors, Moisture, Balance Sulfate100%

Example III Cellulosic Polymers Used in Test Compositions

The representative modified cellulosic polymers used in the liquid andgranular detergent compositions described in Examples I and II arecharacterized in Table C. The various substituents listed are those fromStructural Formulas Nos. I, II and III described hereinbefore.

TABLE C Cellulosic Polymers Used in Test Detergent Compositions PolymerID Polymer Description A B C D Polymer Tradename Polysurf LK-400 CMCModified LK-400 67 (D72) Polymer Manufacturer Hercules Union CarbidePenn Union Carbide Carbose Polymer Type Nonionic Cationic AnionicCationic Molecular Weight 700-750M ˜400M ˜300M ˜400M Structure No. I IIIII II R Cetyl H CH₂COO H (C₁₆) A Amount of Ring Alkyl 0.4%- 0 0 0Substitution 0.6% Degree of Ring — — 0.5 — Carboxymethyl Substitution R¹H — — — R² — —CH₂CH(OH)CH₂— — —CH₂CH(OH)CH₂— R³ — —CH₃ — —CH₃ R⁴ — —CH₃— —CH₃ R⁵ — —CH₃ — —CH₃ R⁶ — H — H x 1-3 1-3 — 1-3 y — ˜0.1 — ˜0.006 Z —Cl⁻ — Cl⁻ A — — Na —

Test compositions prepared as described in Examples I and II areevaluated for the effects that the various cellulosic polymers ofExample III provide when samples of fabrics or garments are washed usingthe test compositions as described, all under identical conditions. Acontrol sample with no polymer is usually compared to one compositionwith a test polymer to be evaluated. Testing conditions are alsocarefully monitored. Examples of controlled conditions include: washtime, wash water temperature and hardness; washer agitation; rinse time,rinse water temperature and hardness; dryer time and temperature; washload fiber content and weight.

Example IV Overall Appearance

In an Overall Appearance test, fabrics are washed using various testcompositions containing either no cellulosic polymers or one of theExample III cellulosic polymers. The fabrics so washed after ten cyclesare then comparatively graded by three judges who evaluate the overallappearance of the washed fabrics. It is the decision of the judge as towhat is to be evaluated unless specific direction is given to evaluateone attribute such as color, pilling, fuzz, etc.

In the Overall Appearance test, the visual preference of the judge isexpressed using the Scheff scale.

That is:

0=No difference

1=I think this one is better (unsure).

2=I know this one is a little better.

3=I know this one is a lot better.

4=I know this one is a whole lot better.

For the Overall Appearance test, laundering conditions are as follows:

Washer Type: Kenmore (17 gallons)

Wash Time: 12 min

Wash Temperature: 90° F. (32.2° C.)

Wash Water Hardness: 6 grains per gallon

Washer Agitation: normal

Rinse Time: 2 min

Rinse Temperature: 60° F. (15.6° C.)

Rinse Water Hardness: 6 grains per gallon

Wash Load Fabric Content: various colored and white garments and fabrics

Wash Load Weight: 5.5 lbs (2.5 kg)

The average overall appearance test results are shown in Tables D and E.

TABLE D Overall Appearance Test Results Overall Appearance Liquid TestComposition ID Polymer Tested Grade Control None 0 A Polysurf 67 1.5 BLK-400 1.8 C CMC (D72) 1.0 D Modified LK-400 1.2

TABLE E Overall Appearance Test Results Granular Test CompositionOverall Appearance ID Polymer Tested Grade Control None 0 A Polysurf 671.4 B LK-400 1.0 C CMC (D72) 1.0 D Modified LK-400 1.1

Example V Pill Reduction

In a Pill Reduction test, fabrics are washed using the various testcompositions containing either no cellulosic polymers or one of theExample III cellulosic polymers. The fabrics so washed are then gradedfor Pill Reduction using a computer-assisted pilling image analysissystem which employs image analysis to measure the number of pills ontested garments and fabrics. Pill reduction is calculated as:

Pill reduction(%)={[# pills (control)−# pills (polymers)]/# pills(control)}×100%

For the Pill Reduction test, laundering conditions are the same as usedfor the Overall Appearance test described hereinbefore in Example IV.

The average % Pill Reduction test results are shown in Tables F and G.

TABLE F Pill Reduction Test Results - Liquids Liquid Test Composition IDPolymer Tested Pill/Fuzz Reduction (%) Control None 0 A Polysurf 67 21.5B LK-400 42.4 C CMC (D72) 26.8 D Modified LK-400 25.9

TABLE G Pill Reduction Test Results - Granular Granular Test CompositionPill/Fuzz Reduction ID Polymer Tested (%) Control None A Polysurf 6733.3 B LK-400 51.6 C CMC (D72) 7.6 D Modified LK-400 16.6

Example VI Color Protection

In a Color Protection test, fabrics are washed using various testcompositions containing either no cellulosic polymers or one of theExample III cellulosic polymers. The fabrics so washed are then testedwith a Hunter calorimeter in order to determine a Delta E* value foreach fabric tested. Delta E* is defined as the color difference(reflectance intensity, hue shift, etc.) between washed fabrics andunwashed fabrics.

For the Color Protection test, laundering conditions are the same asused for the Overall Appearance test described hereinbefore in ExampleIV.

The extent of Color Protection provided is based on percent of Delta E*difference compared to an unwashed sample. Color protection iscalculated as:

% Color Protection={[dE*(control)−dE*(polymers)]/dE*(control)}×100%

The average color protection test results are shown in Tables H and I.

TABLE H Color Protection Test Results - Liquids Liquid Test CompositionID Polymer Tested Color Protection (%) Control None 0 A Polysurf 67 24.2B LK-400 36.5 C CMC (D72) 26.6 D Modified LK-400 27.2

TABLE I Color Protection Test Results - Granular Granular TestComposition ID Polymer Tested Color Protection (%) Control None 0 APolysurf 67 33.9 B LK-400 39.2 C CMC (D72) 15.5 D Modified LK-400 24.7

What is claimed is:
 1. A laundry detergent composition which impartsfabric appearance benefits selected from pill/fuzz reduction,antifading, improved abrasion resistance and/or enhanced softness tofabrics and textiles laundered in aqueous washing solutions formedtherefrom, which composition comprises: A) from about 1 to 80% by weightof a detersive surfactant; B) from about 0.1% to 80% by weight of anon-phosphorus organic or inorganic detergency builder which is a memberselected from the group consisting of zoolite, combinations of zeoliteand sodium carbonate, silicate, an alkali metal salt of a polyhydroxysulfonate, or of a carboxylate or polycarboxylate builder selected fromthe group consisting of nitrilotriacetic acid, oxydisuccinic acid,mellitic acid, a benzene polycarboxylic acid, a polyacetal carboxylate,and mixtures of said non-phosphorus builders; C) from about 0.1% to 8%by weight of a modified cellulose ether fabric treatment agent selectedfrom the group consisting of: i) hydrophobically-modified, nonioniccellulose ethers which have a molecular weight of from about 10,000 to2,000,000 and which have repeating substituted anhydroglucose unitscorresponding to the general formula:

wherein: R is a combination of H and C₈-C₂₄ with alkyl substitution ofthe anhydroglucose rings ranging in an amount of from about 0.1% to 5%by weight of the cellulose ether material; R₁ is H or methyl; and xranges from about 1 to 20; ii) cationic quaternary ammonium celluloseethers which have a molecular weight of from about 10.000 to 2,000,000and which have repeating substituted anhydroglucose units correspondingto the general formula:

wherein: R is H or C₈-₂₄, with alkyl substitution of the anhydroglucoserings ranging in an amount of from about 0.1% to 5% by weight of thecellulose ether material; R₂ is CH₂CHOHCH₂ or C₈-₂₄ alkyl; R₃, R₄ and R₅are each, independently, methyl, ethyl or phenyl; R₆ is H or methyl; xranges from about 1 to 20; y ranges from about 0.005 to 0.5; and Z isCl⁻ or Br⁻; iii) anionic cellulose ethers which have a molecular weightof from about 10,000 to 2,000,000 and which have repeating substitutedanhydroglucose units corresponding to the general formula:

wherein: R is a combination of H and a) CH₂COOA, and, optionally, b) C2⁻²⁴ alkyl, with alkyl substitution of the anhydroglucose rings rangingin an amount of from about 0.1% to 5% by weight of the cellulose ethermaterial, and with the degree of carboxymethyl substitution of theanhydroglucose rings ranging from about 0.05 to 2.5; and wherein A is Naor K; and iv) combinations of said nonionic, cationic and anioniccellulose ethers.
 2. A composition according to claim 1 wherein A) thedetersive surfactant comprises from about 5% to 50% by weight and isselected from anionic and nonionic surfactant materials; and B) themodified cellulose ether fabric treatment agent comprises from about0.5% to 4% by weight of the composition and has a molecular weightranging from 10,000 to 1000,000.
 3. A composition according to claim 2wherein the modified cellulose ether fabric treatment agent is ahydrophobically-modified, nonionic material corresponding to StructuralFormula No. I wherein a) R is a combination of H and C₈ to C₁₆ alkyl, b)R substitution of the anhydroglucose rings ranges from about 0.2% to 2%by weight of the cellulose ether; c) R¹ is H; and d) x ranges from about1 to
 10. 4. A composition according to claim 2 in liquid form whichcomprises a) from about 5% to 50% by weight of a detersive surfactantselected from i) sodium, potassium and ammonium alkylsulfates whereinthe alkyl group contains from 10 to 22 carbon atoms; ii) sodium,potassium and ammonium alkylpolyethoxylate sulfates wherein the alkylgroup contains from 10 to 22 carbon atoms and the polyethoxylate chaincontains from 1 to 15 ethylene oxide moieties; iii) polyhydroxy fattyacid amides of the formula

wherein R is a C₉-₁₇ alkyl or alkenyl and Z is glycityl derived from areduced sugar or alkoxylated derivatives therof; iv) alcohol ethoxylatesof the formula R¹(OC₂H₄)_(n)OH wherein R¹ is a C₁₀-C₁₆ alkyl group or aC₈-C₁₂ alkyl phenyl group and n is from about 3 to 80; and v)combinations of these surfactants; and b) from about 1% to 10% by weightof a detergent builder component selected from said carboxylate andpolycarboxylate builders.
 5. A composition according to claim 2 ingranular form which comprises a) from about 5% to 50% by weight of adetersive surfactant selected from i) sodium and potassiumalkylpolyethoxylate sulfates wherein the alkyl group contains from 10 to22 carbon atoms and the polyethoxylate chain contains from 1 to 15ethylene oxide moieties; ii) sodium and potassium C₉ to C₁₅ alkylbenzene sulfonates; iii) sodium and potassium C₈ to C₁₈ alkyl sulfates;iv) polyhydroxy fatty acid amides of the formula

wherein R is a C₉-₁₇ alkyl or alkenyl and Z is glycityl derived from areduced sugar or alkoxylated derivatives thereof; and v) combinations ofthese surfactants; and b) from about 1% to 50% by weight of a detergentbuilder selected from the group consisting of, zeolite, combinations ofzeolite and sodium carbonate, silicate, oxydisuccinates, citrates, andmixtures thereof.